US8020435B2 - Method of investigating a coated surface of an object - Google Patents
Method of investigating a coated surface of an object Download PDFInfo
- Publication number
- US8020435B2 US8020435B2 US11/914,846 US91484606A US8020435B2 US 8020435 B2 US8020435 B2 US 8020435B2 US 91484606 A US91484606 A US 91484606A US 8020435 B2 US8020435 B2 US 8020435B2
- Authority
- US
- United States
- Prior art keywords
- coating
- colour
- tight
- potential
- change
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/8422—Investigating thin films, e.g. matrix isolation method
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/8803—Visual inspection
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/89—Investigating the presence of flaws or contamination in moving material, e.g. running paper or textiles
- G01N21/8914—Investigating the presence of flaws or contamination in moving material, e.g. running paper or textiles characterised by the material examined
- G01N2021/8918—Metal
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/89—Investigating the presence of flaws or contamination in moving material, e.g. running paper or textiles
- G01N21/892—Investigating the presence of flaws or contamination in moving material, e.g. running paper or textiles characterised by the flaw, defect or object feature examined
- G01N21/894—Pinholes
Definitions
- the present invention relates to a method of investigating a coated surface of an object in order to determine whether or not the coated surface is tight, in particular in order to determine whether or not the coated surface comprises pinholes. More particularly, the present invention relates to an easy and visual method of determining whether or not pinholes are present in a coated surface of an object. The method of the present invention is particularly suitable for investigating objects having a coating of tantalum or an alloy of tantalum.
- a corrosive resistant coating to objects having an intended use in a relatively hostile and/or corrosive environment. This is, e.g., the case for objects which are used as implants.
- coatings of refractory metals, such as niobium or tantalum are frequently used on objects made from steel or other metals or alloys. Since a coating as described above will typically have a higher corrosion potential than the substrate material positioned below the coating, the coating will only eliminate corrosion if the coating is tight. If this is not the case, e.g. because the coating contains pinholes, there is a risk of pitting.
- coated surfaces have been investigated in order to detect possible pinholes by inserting the object in a circuit comprising a current source and an ammeter. If a reading can be obtained on the ammeter, the coated surface is conductive and thereby tight. This method is relatively time consuming and expensive since it requires the use of a current source and an ammeter each time it is desired to investigate whether or not the coating of an object is tight.
- JP 57132045 One method of investigating a coated surface in order to visually detect the presence of possible pinholes is described in JP 57132045.
- a coated surface of a metallic material as a cathode opposite to an anode is positioned in an electrolyte containing a solution type electrochromic material, such as a viologen dye.
- a voltage is applied to the cathode, thereby causing an electrolytic reduction of the viologen dye from a colourless dication I to an insoluble monocation radical II.
- the insoluble monocation II is deposited in pinhole parts in a red or reddish purple colour.
- the presence or absence of pinholes is detected with an ammeter.
- an object of the present invention to provide a method of visually detecting possible pinholes in a coated surface of an object in a reliable manner.
- the above and other objects are fulfilled by providing a method of investigating a coated surface of an object, the coating material comprising a metal or an alloy, the method comprising the steps of:
- the colour of the coating changes over at least a substantial part of the object if the coating is at least substantially tight, a relatively dramatic visual effect is obtained. Thereby it is very easy to immediately determine by visual inspection whether or not the coating is tight. This is even possible for an end user of the object. Furthermore, the dramatic effect provides a very reliable detection of whether or not the coating is tight. Finally, the detection of the pinholes is purely visual, and the need for additional equipment is accordingly avoided.
- the resulting object may advantageously be used in applications where it is important that the coating is tight. As mentioned above, this is, e.g., the case for objects which it is intended to position in highly corrosive environments. Implants are an example of such objects.
- the change in colour or lack of change in colour is provided in the following manner.
- an increasing potential to the object, it will be attempted to obtain the desired current level.
- the coating is at least substantially tight it will not be possible to conduct a current of a sufficient current level because the tight coating is not conductive. Therefore the applied potential will continue to increase until the maximum potential is reached.
- the relatively high potential which is thereby applied to the object will cause the change in colour, thereby indicating that the coating is at least substantially tight.
- the coating is not tight, e.g. if the coating comprises one or more pinholes, the applied potential will result in a localized corrosion attack in the region(s) of the pinhole(s). Thereby it is possible to conduct a current at the desired current level. When this occurs the increase in potential will stop, and the applied potential will therefore not be sufficient to cause a change in colour.
- the desired current level will depend on the total surface area of the object. However, the current density of the desired current is preferably within the interval 0.0001 mA/cm 2 to 0.1 mA/cm 2 , preferably within the interval 0.001 mA/cm 2 to 0.01 mA/cm 2 .
- the maximum potential is preferably within the interval 10 V to 30 V, such as within the interval 15 V to 25 V, such as 16 V or 24 V.
- the step of applying an increasing potential is preferably performed while the object is positioned in a liquid medium.
- the liquid medium may be any medium which the coating material is resistant in (i.e. the corrosion rate is less than 50 mpy (mils per year), preferably less than 2 mpy), and which has a conductivity of at least 10 S ⁇ cm 2 , preferably at least 100 S ⁇ cm 2 .
- a tantalum coated object having a total surface area of 800 cm 2 was positioned in a test solution of 1% sulphuric acid at room temperature.
- the object was connected to a power supply capable of providing maximum potentials of 16 V or 24 V.
- the applied potential was increased from 0 V in an attempt to let the voltage stabilise at a fixed current density of 0.005 mA/cm 2 , corresponding to a current level of 4 mA. If this was not possible the applied potential was allowed to increase to the maximum value, i.e. 16 V or 24 V.
- For a tight coating and a maximum potential of 16 V the object turned brown after 5 minutes.
- For a tight coating and a maximum potential of 24 V the object turned blue after 5 minutes.
- no change in colour was observed after 30 minutes.
- the method is preferably performed at a temperature within the interval 0° C. to 120° C., such as within the interval 10° C. to 90° C., preferably at room temperature, i.e. approximately 20° C.
- the step of applying an increasing potential to the object may be performed in such a way that the coating is at least partly polarized due to the high maximum potential if the coating is at least substantially tight, thereby causing the change in colour of the coating.
- the applied maximum potential should be sufficient to cause the desired change in colour when this polarization occurs, as described above.
- a selective corrosion of the underlying substrate material will occur, causing the coating to become conducting. It will therefore not be possible to obtain a sufficient overvoltage/potential to obtain a change in colour, and the colour of the object will therefore remain the original colour of the object, i.e. the natural colour of the coating material. Thereby the colour of the resulting object becomes an indicator for whether or not the coating was tight at the time the increasing potential was applied.
- the step of applying an increasing potential to the object may cause an increase in thickness of a naturally occurring metal oxide layer on the coating, said increase in thickness in turn providing the change in the colour of the coating if the coating is at least substantially tight.
- the increase in thickness may be caused by a polarization of the coating as described above.
- the increase in thickness may result from a temperature effect or due to the object being positioned in an oxidizing medium.
- Such an increase in thickness of a metal oxide layer will, furthermore, be advantageous in case the coating layer is perforated at a later time, because the oxide layer has an insulating effect and prevents electrochemical half-reactions on the surface of the coating. Thereby galvanic (accelerated) corrosion of the substrate material will not be possible.
- an oxide layer of an increased thickness may provide the object with improved wear resistance and/or improved tribilogical properties.
- the coating material may be or comprise a refractory metal or an alloy of a refractory metal, such as tantalum or an alloy of tantalum.
- the coating material could be or comprise any other suitable refractory metal, such as niobium, molybdenum, zirconium, tungsten or an alloy of one or more of these metals.
- the coating material may be or comprise any other suitable metal or alloy, e.g. titanium, as long as the coating is electrically conductive, and as long as it is possible to change the colour of the coating material by applying an increasing potential to the object.
- the coating material is or comprises tantalum or an alloy of tantalum, the change in colour will in most cases be such that the resulting object obtains a distinct blue colour if the coating is at least substantially tight.
- the step of applying an increasing potential to the object may be performed by means of a galvanostat. Since a galvanostat is adapted to apply a specific current (as opposed to a specific voltage) this is very suitable in case a current of a predetermined level is desired as described above.
- the change in colour in case the coating is at least substantially tight is performed in an at least substantially permanent manner.
- the term ‘at least substantially permanent’ should in this context be interpreted as an effect which remains for a relatively long period of time, preferably until the outer layer is physically worn off.
- a substantially permanent effect is, e.g., obtained when the change in colour originates from a polarization of the coating material.
- the changed colour remains at least substantially permanently it is immediately possible for an end user to determine whether or not the coating is at least substantially tight.
- the change in colour is at least substantially permanent, the changes in the coating causing the change in colour will probably also be at least substantially permanent. Such changes will often have a beneficial effect on the corrosive properties of the object which will thereby be improved.
- the invention further relates to an object having a coating, the colour of the coating being provided using the method described above. Since the colour of such an object reveals whether or not the coating is tight, an end user will be able to immediately see this, and thereby determine whether or not the object at hand has the desired corrosive resistant properties. Furthermore, as described above the object may further be at least partly protected from corrosion in case the coating is perforated at a later time.
- FIG. 1 is a schematic drawing of an object positioned in an electrolyte prior to applying an increasing potential to the object
- FIG. 2 is a schematic drawing of the object of FIG. 1 after an increasing potential has been applied to the object.
- FIG. 1 is a schematic drawing of an object 1 which is positioned in an electrolyte 2 .
- the object 1 is coated with a coating material comprising a metal or an alloy, and it is desired to investigate, in accordance with the present invention, whether or not the coating is tight.
- the object 1 is connected in series to a potential source 3 in the form of a galvanostat, which in turn is connected in series to the walls 4 of a container holding the electrolyte.
- a potential source 3 When the potential source 3 is switched on, an increasing potential will be applied to the object 1 in an attempt to obtain a desired current level. If the coating is at least substantially tight, the coating will not be conductive, and it will therefore not be possible to obtain the desired current level. The potential will therefore continue to increase until a maximum potential is reached. This high potential causes the coating to become polarized, and as a result the colour of the coating will change.
- FIG. 2 is a schematic drawing of the object 1 of FIG. 1 .
- the potential source 3 has previously been switched on, and because the coating of the object 1 is at least substantially tight, the colour of the coating has changed as described above. If, on the other hand, the coating of the object 1 is not at least substantially tight, the coating will be conductive as previously explained, at it will therefore be possible to conduct a current at the desired current level. When this happens the increase in potential will be stopped, and the potential applied to the object 1 will therefore not be sufficient to cause a change in colour.
- the colour of the coating changes from grey to blue. Thereby it is very easy for an end user of the object 1 to determine whether or not the coating is at least substantially tight. If the object 1 appears blue, the coating is at least substantially tight, and if the object 1 appears grey the coating is not tight.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Automation & Control Theory (AREA)
- Mathematical Physics (AREA)
- Biodiversity & Conservation Biology (AREA)
- Ecology (AREA)
- Environmental & Geological Engineering (AREA)
- Environmental Sciences (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
-
- applying an increasing potential to the object until a desired current level has been obtained or until a maximum potential has been reached,
- visually inspecting the object, and
- in case the colour of the coating has changed over at least a substantial part of the object, determining that the coating is at least substantially tight, or
- in case the colour of the coating has not changed over at least a substantial part of the object, determining that the coating is not tight.
Claims (8)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK200500739 | 2005-05-20 | ||
| DKPA200500739 | 2005-05-20 | ||
| DKPA200500739 | 2005-05-20 | ||
| PCT/DK2006/000270 WO2006122559A1 (en) | 2005-05-20 | 2006-05-18 | A method of investigating a coated surface of an object |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20080280027A1 US20080280027A1 (en) | 2008-11-13 |
| US8020435B2 true US8020435B2 (en) | 2011-09-20 |
Family
ID=36764730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/914,846 Expired - Fee Related US8020435B2 (en) | 2005-05-20 | 2006-05-18 | Method of investigating a coated surface of an object |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US8020435B2 (en) |
| EP (1) | EP1902299A1 (en) |
| CN (1) | CN101175985A (en) |
| WO (1) | WO2006122559A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014006723B4 (en) * | 2014-05-07 | 2023-01-26 | Mercedes-Benz Group AG | Methods for visualizing and cleaning contamination |
| CN104297299B (en) * | 2014-09-10 | 2017-03-08 | 中昊晨光化工研究院有限公司 | A kind of outer wall is the quality determining method of the non-conductive coated inside of lining pipe of metal |
| CN112921383B (en) * | 2021-01-20 | 2022-09-16 | 珠海松柏科技有限公司 | Electroplating production equipment and instant starting method of rectifier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3619385A (en) | 1968-02-05 | 1971-11-09 | Nadezhda Vasilievna Rjumshina | Process for manufacturing an article with a polychrome picture imposed on the surface thereof |
| SU473936A1 (en) | 1971-08-02 | 1975-06-14 | Предприятие П/Я А-7291 | Method for corrosion testing of zirconium alloys |
| JPS57132045A (en) | 1981-02-09 | 1982-08-16 | Seiko Epson Corp | Pin hole tester |
| GB2400113A (en) | 2003-03-31 | 2004-10-06 | Univ Sheffield Hallam | Layers Having Interference Effect |
-
2006
- 2006-05-18 US US11/914,846 patent/US8020435B2/en not_active Expired - Fee Related
- 2006-05-18 EP EP06742425A patent/EP1902299A1/en not_active Withdrawn
- 2006-05-18 CN CNA2006800169969A patent/CN101175985A/en active Pending
- 2006-05-18 WO PCT/DK2006/000270 patent/WO2006122559A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3619385A (en) | 1968-02-05 | 1971-11-09 | Nadezhda Vasilievna Rjumshina | Process for manufacturing an article with a polychrome picture imposed on the surface thereof |
| SU473936A1 (en) | 1971-08-02 | 1975-06-14 | Предприятие П/Я А-7291 | Method for corrosion testing of zirconium alloys |
| JPS57132045A (en) | 1981-02-09 | 1982-08-16 | Seiko Epson Corp | Pin hole tester |
| GB2400113A (en) | 2003-03-31 | 2004-10-06 | Univ Sheffield Hallam | Layers Having Interference Effect |
Non-Patent Citations (2)
| Title |
|---|
| C.G. Granqvist, Electrochromic devices, Journal of the European Ceramic Society 25 (2005) 2907-2912. |
| PCT Search Report for Serial No. PCT/DK2006/000270 dated Aug. 30, 2006. |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1902299A1 (en) | 2008-03-26 |
| WO2006122559A1 (en) | 2006-11-23 |
| CN101175985A (en) | 2008-05-07 |
| US20080280027A1 (en) | 2008-11-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: DANFOSS A/S, DENMARK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GILLESBERG, BO;REEL/FRAME:021442/0991 Effective date: 20080414 |
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| STCF | Information on status: patent grant |
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| AS | Assignment |
Owner name: TANTALINE A/S, DENMARK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DANFOSS A/S;REEL/FRAME:028290/0102 Effective date: 20120525 |
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Owner name: TANTALINE CVD HOLDING APS, DENMARK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TANTALINE A/S;REEL/FRAME:041799/0866 Effective date: 20170317 |
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